Regioselective 1,2-Hydrogen Atom Transfer of N-Centered Radicals for C(sp 3 )–C(sp 3 ) Coupling to Generate 1,2-Diamine Derivatives

Organic Letters 2026

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Authors: Yu Pan, Hai‐Tao Yang, Yifeng Bai, Kaili Yu, Shiyu Huang, Zihan Zhang, Hongbin Zhang, Shixi Liu, Guogang Deng, Xiaodong Yang
DOI: 10.1021/acs.orglett.6c00406
Cited by: 3
References: 29

Abstract

Herein, 2-azaallyl anions are reported as super electron donors (SEDs) in the reduction of N -chlorodialkylamines to generate N-centered radicals (NCRs). The NCRs undergo regioselective net 1,2-hydrogen atom transfer (1,2-HAT) to yield C-centered radicals, which subsequently participate in C(sp 3 )–C(sp 3 ) intermolecular radical cross-coupling with 2-azaallyl radicals, culminating in the generation of 1,2-diamine derivatives (30 examples, up to 85% yield). A telescoped gram-scale synthesis and hydrolysis of the product demonstrated the synthetic potential of this method. Mechanistic investigations, including radical trapping, radical clock experiments, and density functional theory calculations, provide significant evidence for an intramolecular radical net 1,2-HAT pathway.

Fields of Study & Subjects

Radical Photochemical Reactions Catalytic C–H Functionalization Methods Metalloenzymes and iron-sulfur proteins

Publication details

Journal / source
Organic Letters
Publisher
American Chemical Society (ACS)
Volume
28
Issue
8
Pages
2795–2800
Publication date
16 February 2026
Language
EN